US8911851B2 - Latent-reactively glued TPU/PC layer materials - Google Patents

Latent-reactively glued TPU/PC layer materials Download PDF

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US8911851B2
US8911851B2 US13/125,077 US200913125077A US8911851B2 US 8911851 B2 US8911851 B2 US 8911851B2 US 200913125077 A US200913125077 A US 200913125077A US 8911851 B2 US8911851 B2 US 8911851B2
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layers
protective layers
core layer
polymer
protective
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US20110274883A1 (en
Inventor
Reinhard Löwe
Per Krüger
Michael Knebel
Jens Ehreke
Heinz Pudleiner
Mehmet-Cengiz Yesildag
Klaus Meyer
Dirk Pophusen
Jörg Büchner
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Covestro Deutschland AG
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Bayer MaterialScience AG
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    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
    • G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
    • G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
    • G06K19/067—Record carriers with conductive marks, printed circuits or semiconductor circuit elements, e.g. credit or identity cards also with resonating or responding marks without active components
    • G06K19/07—Record carriers with conductive marks, printed circuits or semiconductor circuit elements, e.g. credit or identity cards also with resonating or responding marks without active components with integrated circuit chips
    • G06K19/077—Constructional details, e.g. mounting of circuits in the carrier
    • G06K19/07745—Mounting details of integrated circuit chips
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
    • Y10T156/1039—Surface deformation only of sandwich or lamina [e.g., embossed panels]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • Y10T428/24612—Composite web or sheet
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/266—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension of base or substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31721—Of polyimide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31931—Polyene monomer-containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • the invention relates to a security and/or valuable document comprising an inlay, which includes a core layer, the electronic components, and/or diffractive security elements, and polymer layers, into which the inlay is laminated.
  • the invention further relates to a method for producing such a security and/or valuable document
  • Security and/or valuable documents such as identity cards, passports, access allowance cards, visas, tickets, driver licenses, vehicle documents, personalized valuables, credit cards, or personalized chip cards increasingly comprise electronic circuits and other active and passive electronic components, such as integrated semiconductors (ICs), but also chip modules, displays, batteries, coils, capacitors, contact spots etc.
  • ICs integrated semiconductors
  • PC polycarbonate
  • thermoelastic and/or thermoplastic protective layers for instance thermoplastic polyurethane (TPU)
  • TPU thermoplastic polyurethane
  • these adhesive layers are however a point of weakness of the card structure. Through the edge of the card, water vapor and air can more easily diffuse in and thus lead to a later delamination. Other environmental effects, too, in particular high temperatures, but also fast temperature changes may lead to that the card is split and therefore cannot be used anymore.
  • volume holograms are difficult to handle or not at all on an industrial scale and are inflexible, if e.g. cavities are to be filled up. Similar considerations apply for components with diffractive structures, e.g. volume holograms. If the hologram is directly laminated with other PC films so to form a card, this occurs in certain cases under losses being quantifiable visually and by machine of the display quality of the hologram, in particular of the colors and of the 3-dimensional appearance. Most volume holograms based on photopolymer namely have a softening point or a glass temperature T g of clearly below 150° C.
  • the Bragg planes are shifted, and certain elements appear shifted in wavelength. For instance, green picture elements become yellow picture elements, etc.
  • the 3-dimensional impression is distinctly reduced, and the holograms appear rather flat and 2-dimensional and washed out.
  • the base polymers used for the protective layers have different structures from the polycarbonate preferred for the other polymer layers, so that a substance-to-substance connection is sometimes not achieved during the lamination. There is, therefore, here too the risk of delamination. Consequently, there is an increased risk of counterfeit and/or manipulation, since the inlay can possibly be removed in a non-destructive manner and can be incorporated in a different layer composite, a counterfeit. Furthermore, data that the inlay carries or comprises can be manipulated.
  • latent-reactive adhesives are known in the art, and as an example only reference is made to the document EP 0 922 720 A1.
  • FIG. 1 illustrates a diagrammatical representation of a security and/or valuable document produced according to the invention.
  • the invention teaches a security and/or valuable document comprising electronic components and/or diffractive security elements, at least one protective layer being arranged on one side or two protective layers being arranged on both sides of the electronic components and/or of the diffractive security element, said protective layers being formed of a first base polymer, polymer layers being formed of a second base polymer being different from the first base polymer, into said polymer layers the electronic components and/or the diffractive security element with the protective layers being laminated, adhesive layers with a latent-reactive adhesive being arranged at least between the polymer layers and the protective layers.
  • Latent-reactive adhesives per se are known in many different ways. For this purpose, for instance reference is made to the document EP 0 922 720. According thereto, they are substantially aqueous dispersions with at least one surface-deactivated polyisocyanate and at least one polymer reactive with isocyanate.
  • the deactivated polyisocyanates have reaction temperatures in the range from 30° C. to 180° C., in particular 40° C. to 150° C.
  • the melting points thereof are in the range from 40° C. to 150° C.
  • polyisocyanates this term also includes diisocyanates
  • aliphatic, cycloaliphatic, heterocyclic or aromatic polyisocyanates are suitable, for instance diphenylmethane-4,4′-diisocyanate, naphthalene-1,5-diisocyanate, 3,3′-dimethyl-biphenyl-4,4′-diisocyanate, dimeric 1-methyl-2,4-phenylene-diisocyanate, 3,3′-diisocyanate-4,4′-dimethyl-N,N′-diphenylurea, the addition product of 2 moles 1-methyl-2,4-phenylene-diisocyanate with 1 mole 1,2-ethandiol, 1,4-butandiol, 1,4-cyclohexan-di-methanol, or ethanolamine, the isocyanurate of the IPDI.
  • the reaction temperature is below 90° C.
  • Reaction partners of the polyisocyanates may be water-soluble or water-dispersible emulsion or dispersion polymers, which carry isocyanate-reactive groups, such as for instance hydroxyl, amino, carboxyl, or carbon amide groups.
  • the proportion of monomers with isocyanate-reactive groups typically is in the range from 0.2 to 15 wt. %, in particular 1 to 8 wt. %, referred to the polymer.
  • Suitable monomers are: allyl alcohol, hydroxyethyl or hydroxypropyl acrylate and methacrylate, butandiol monoacrylate, ethoxylated or propoxylated acrylates or methacrylates, N-methylol acrylamide, tert butyl amino ethyl methacrylate, acrylic, and methacrylic acid, maleic acid, maleic acid monoester. Furthermore, the copolymerization of glycidyl methacrylate and/or allyl glycidyl ether is possible.
  • They contain an epoxy group, which is derivatized in a further step with amines or amino alcohols to a secondary amine, for instance with ethylamine, ethyl hexylamine, isononylamine, aniline, toluidine, xylidine, benzylamine, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 2-(2-aminoethoxy) ethanol.
  • amines or amino alcohols to a secondary amine
  • ethylamine ethyl hexylamine
  • isononylamine aniline
  • toluidine xylidine
  • benzylamine ethanolamine
  • 3-amino-1-propanol 1-amino-2-propanol, 5-amino-1-pentanol, 6-amino-1-hexano
  • Suitable are further water-soluble binding agents, such as polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, hydroxyethyl cellulose, hydroxypropyl cellulose, or also water-dispersible hydroxy-functional polyesters, hydroxy-functional sulfo-polyesters, and polyurethane dispersions, dispersions of polyamidoamines, which carry carboxyl-hydroxyl-primary or secondary amino groups.
  • aqueous colloidal dispersions or colloidal solutions with particle sizes between 1 and 100 nm based on thermoplastic polymers with isocyanate-reactive groups, such as for instance (higher-molecular) solid epoxy resins, poly-ethylene-vinyl alcohol or polyethylene-co-acryl acid can be used.
  • the ratio of the isocyanate groups to the sum of the isocyanate-reactive groups, such as hydroxy or amino, is suitably in the range from 0.1 to 1.5.
  • Means for the surface deactivation of the polyisocyanate particles to be used are primary and secondary aliphatic amines, diamines or polyamines, hydrazine derivatives, aminides, guanidines, such as for instance ethylenediamine, 1,3-propylenediamine, diethylenetriamine, triethylenetetramine, 2,5-dimethylpiperazine, methylnonanediamine, isophoronediamine, 4,4′-diamino dicyclohexyl methane, diamino and triamino polypropylene ether, polyaminoamines and mixtures of mono-, di-, and/or polyamines.
  • primary and secondary aliphatic amines such as for instance ethylenediamine, 1,3-propylenediamine, diethylenetriamine, triethylenetetramine, 2,5-dimethylpiperazine, methylnonanediamine, isophoronediamine, 4,4′-diamino dicyclo
  • the concentration of the deactivation agent should be 0.1 to 25, in particular 0.5 to 8 equivalent percent, referred to all present isocyanate groups.
  • the polyisocyanate particles may be surface-deactivated by reaction with the deactivation agent before, during or after grinding to a particle size of for instance less than 500 ⁇ m, in particular less than 100 ⁇ m, preferably less than 50 ⁇ m.
  • the adhesive may further comprise catalysts, which control the surface deactivation or reactivation and/or the cross-linking reaction of the polyisocyanate with the polymer.
  • catalysts which control the surface deactivation or reactivation and/or the cross-linking reaction of the polyisocyanate with the polymer.
  • these are hydrolysis-stable catalysts that accelerate the heat-activated cross-linking reaction, such as for instance the organic tin, iron, lead, cobalt, bismuth, antimony, or zinc compounds or their mixtures known in the urethane catalysis.
  • Preferred are alkyl mercaptide compounds of dibutyl tin.
  • the amount of catalyst is suitably from 0.0001 to 3 wt. %, in particular 0.01 to 1 wt. %, referred to the sum of polyisocyanate and polymer.
  • the adhesive finally may comprise usual inert additions, such as wetting agents, organic or inorganic thickening agents, softening agents, filling agents, plastic powders, pigments, dyes, UV stabilizers, radical scavengers, corrosion inhibitors, flame retardants, propellants, and/or inert organic solvents.
  • inert additions such as wetting agents, organic or inorganic thickening agents, softening agents, filling agents, plastic powders, pigments, dyes, UV stabilizers, radical scavengers, corrosion inhibitors, flame retardants, propellants, and/or inert organic solvents.
  • a layer of an adhesive used according to the invention can be produced by that an aqueous dispersion or solution of the components described above is prepared, and is then applied on a substrate. Then takes place a removal of the water at temperatures below the reaction temperature of the polyisocyanate.
  • a layer of an adhesive used according to the invention may as such already have an adhesive effect. It is however essential that when heating the layer above a reaction temperature T r the isocyanate is reactivated and reacts with other functional groups in the adhesive, but in particular also in polymers, with which the adhesive is in contact, and thus forms a substance-to-substance and not easily separable connection.
  • the protective layers are protected by the protective layers against damage during the lamination. Further, by using the latent-reactive adhesive, it is achieved that the protective layers can be integrated safely and inseparably in a security and/or valuable document, although the protective layers are formed of a base polymer, which cannot easily be laminated with the polymer layers, for instance PC.
  • the electronic components and/or the diffractive security element can be used quasi freestanding, or can be embedded in a core layer, and then optionally adhesive layers with a latent-reactive adhesive can be arranged between the protective layers and the core layer, too.
  • the core layer can be formed of a thermoplastic elastomer, in particular selected from the group comprising “olefin-based thermoplastic elastomers (TPO), mainly PP/EPDM, e.g. Santoprene, cross-linked olefin-based thermoplastic elastomers (TPV), e.g. PP/EPDM, e.g. Sarlink (DSM), urethane-based thermoplastic elastomers (TPU), e.g. Desmopan, Texin (Bayer), thermoplastic copolyesters (TPE), e.g.
  • TPO olefin-based thermoplastic elastomers
  • TPV cross-linked olefin-based thermoplastic elastomers
  • TPV cross-linked olefin-based thermoplastic elastomers
  • TPV cross-linked olefin-based thermoplastic elastomers
  • DSM cross-linked olefin-based thermo
  • Hytrel DuPont
  • SBS styrene block copolymers
  • SEBS styrene block copolymers
  • SEPS styrene block copolymers
  • MBS e.g. Septon (Kuraray) or Thermolast K (Kraiburg TPE)
  • thermoplastic copolyamides e.g. PEBA”.
  • thermoplastic polymers having a comparatively high plasticity may also be used.
  • the protective layers may be identical or different and may be formed of a thermoplastic elastomer, in particular selected from the group comprising “olefin-based thermoplastic elastomers (TPO), mainly PP/EPDM, e.g. Santoprene, cross-linked olefin-based thermoplastic elastomers (TPV), e.g. PP/EPDM, e.g. Sarlink (DSM), urethane-based thermoplastic elastomers (TPU), e.g. Desmopan, Texin (Bayer), thermoplastic copolyesters (TPE), e.g.
  • Hytrel DuPont
  • SBS styrene block copolymers
  • SEBS styrene block copolymers
  • SEPS styrene block copolymers
  • MBS e.g. Septon (Kuraray) or Thermolast K (Kraiburg TPE)
  • thermoplastic copolyamides e.g. PEBA.”
  • thermoplastic polymers having a comparatively high plasticity may also be used.
  • the polymer layers may be identical or different and be formed of a base polymer selected from the group comprising “PC (polycarbonate, in particular bisphenol A polycarbonate), PET (polyethylene glycol terephthalate), PET-G, PET-F, PMMA (polymethyl methacrylate), ABS (acrylnitrile butadiene styrene), PE (polyethylene), PP (polypropylene), PI (polyimide or poly-trans-isoprene), PVC (polyvinyl chloride) and copolymers of such polymers”.
  • PC polycarbonate, in particular bisphenol A polycarbonate
  • PET polyethylene glycol terephthalate
  • PET-G PET-F
  • PMMA polymethyl methacrylate
  • ABS acrylnitrile butadiene styrene
  • PE polyethylene
  • PP polypropylene
  • PI polyimide or poly-trans-isoprene
  • PVC polyvinyl chloride
  • the core layer if provided, is formed of a TPE
  • the protective layers are formed of a thermoplastic polyurethane
  • the polymer layers are formed of a PC.
  • the core layer typically has a thickness from 100 to 600 ⁇ m, preferably 200 to 400 ⁇ m.
  • the protective layers typically have a thickness from 30 to 250 ⁇ m, preferably 30 to 150 ⁇ m.
  • the polymer layers typically have a thickness in the range from 30 to 400 ⁇ m, preferably 50 to 250 ⁇ m.
  • One of the protective layers may have a recess, or both protective layers may have recesses.
  • One of the protective layers may immediately carry a printing layer on the side facing the core layer or the electronic component and/or on the side facing away from the core layer or the electronic component, on the entire surface or a partial surface, or both protective layers may each immediately carry a printing layer on the side facing the core layer or the electronic component and/or on the side facing away from the core layer or the electronic component, on the entire surface or a partial surface.
  • the invention also relates to a method for producing a security and/or valuable document according to the invention comprising the following steps: a1) an electronic component or a diffractive security element is provided, or a2) a core layer with embedded electronic components and/or diffractive elements is produced, b) on the core layer and/or on one side of the protective layers, optionally after imprinting at least one of the protective layers, and/or on both sides of the protective layers a latent-reactive adhesive is applied, and c) the core layer, the protective layers and the polymer layers are joined so to form a layer structure of the order “polymer layers, protective layer, electronic component and/or diffractive element or core layer, protective layer, polymer layers” and laminated with each other, said layers being heated to a temperature, which is above a reaction temperature T r of the latent-reactive adhesive.
  • the lamination may be carried out at temperatures in the range from 100 to 230° C., in particular 170 to 210° C., for a time from 1 to 240 min, in particular 5 to 60 min, at a pressure from 0 to 400 N/cm 2 , in particular 10 to 200 N/cm 2 , and optionally under vacuum in the range from 2 to 1000 mbars.
  • the step of compilation of the different polymer layers precedes the lamination process.
  • the compilation can take place in all usual ways, continuously, quasi-continuously or discontinuously.
  • all polymer layers, if applicable including inlay can be guided in parallel to each other, so that only when inserting a roll, the accuracy of fit of all tracks is important.
  • an automatic monitoring of the running accuracy of the tracks and an automatic correction is performed, so that the different polymer layers always move in a given defined position with regard to each other.
  • the lamination of the positioned tracks takes place, for this purpose the lamination of rolls being a particularly efficient and fast method.
  • the lamination of single sheets can also be used.
  • a single sheet has different sections of a polymer layer, which are assigned to different security and/or valuable documents, or consists thereof.
  • document-wise individual lamination can be employed. Therein, for instance electronic circuits can be tested for operation, and printing layers can be tested for freedom of errors, and that before the respective polymer layers are compiled. Thereby, rejects are minimized, since only tested polymer layers are compiled and then joined with each other. There is no need to re-manufacture all polymer layers, if one of the polymer layers is faulty.
  • the use of PC materials is preferred, and for instance for the further polymer layers in particular so called low-T g materials can be used.
  • Low-T g materials are polymers, the glass temperature of which is below 140° C.
  • the further polymer layers are formed of identical or different polymers, the base polymer of the immediately adjacent further polymer layers, comprising identical or different groups being reactive with each other, wherein at a lamination temperature of less than 200° C., reactive groups of the latent-reactive adhesive react with each other and/or with reactive groups of the further polymer layers and form a covalent bond with each other.
  • the lamination temperature can be reduced, without endangering thereby the tight bond of the laminated layers.
  • reactive groups are of course possible. These include the reaction partners of the Diels-Alder reaction or a metathesis.
  • the reactive groups can be bound directly or via a spacer group to the base polymer.
  • Spacer groups include all spacer groups known to the man skilled in the art of polymeric chemistry.
  • the spacer groups may also be oligomers or polymers, which provide elasticity, whereby the risk of breakage of the security and/or valuable document is reduced. Such spacer groups providing elasticity are well known to the man skilled in the art and therefore need not be explained here in detail.
  • base polymer designates in the context of the above explanations a polymeric structure, which does not carry any reactive groups under the employed lamination conditions. These may be homopolymers or copolymers. They also include polymers modified with regard to the mentioned polymers.
  • FIG. 1 shows a diagrammatical representation of a security and/or valuable document produced according to the invention.
  • the core layer 3 consists of a thermoplastic elastomer, for instance olefin-based thermoplastic elastomers (TPO), mainly PP/EPDM, e.g. Santoprene, cross-linked olefin-based thermoplastic elastomers (TPV), e.g. PP/EPDM, e.g. Sarlink (DSM), urethane-based thermoplastic elastomers (TPU), e.g. Desmopan, Texin (Bayer), thermoplastic copolyester (TPE), e.g.
  • TPO thermoplastic elastomer
  • TPO thermoplastic elastomers
  • TPV cross-linked olefin-based thermoplastic elastomers
  • TPV cross-linked olefin-based thermoplastic elastomers
  • TPV cross-linked olefin-based thermoplastic elastomers
  • DSM cross-linked olefin-based thermoplastic
  • Hytrel DuPont
  • SBS styrene block copolymers
  • SEBS styrene block copolymers
  • SEPS styrene block copolymers
  • MBS e.g. Septon (Kuraray) or Thermolast K (Kraiburg TPE)
  • thermoplastic copolyamides e.g. PEBA.
  • protective layers 4 , 5 are provided on both sides of the core layer 3 , said protective layers 4 , 5 being connected by two layers 6 , 7 of a latent-reactive adhesive with the core layer 3 .
  • the protective layers 4 , 5 in this example are formed of a thermoplastic polyurethane.
  • This composite has been laminated into further polymer layers 8 , 9 , 12 , 13 , which are formed of a polycarbonate. Between the protective layers 4 , 5 and the polymer layers 9 , 12 , further layers 10 , 11 with the latent-reactive adhesive are provided.
  • the protective layers 4 , 5 in the composite system are connected in a substance-to-substance manner, so that ultimately a monolithic security and/or valuable document 2 is obtained.
  • the core layer 3 is not essential for the invention and can also be left out without replacement. Then, in the area, where the core layer 3 is drawn, only the electronic components 14 are arranged, and the protective layers 4 , 5 correspondingly come closer together.
  • an adhesive used according to the invention is described.
  • water 33 parts by weight Kelzan S, 3% solution in water (Monsanto), 1 part by weight polyoxyethylene sorbitan trioleate, 2-6 parts by weight polyamine (Euretek 505, (Witco), a polyaminoamine and/or Jeffamine T-403 (Huntsman), an amino-terminated polyoxypropylene) and 80 parts by weight polyisocyanate powder (particle size smaller than 45 ⁇ m)
  • polyisocyanate for instance the IPDI isocyanurate (IPDI-T 1890/100, Hüls) can be used.
  • the other polyisocyanates mentioned above can also be used.
US13/125,077 2008-10-21 2009-07-20 Latent-reactively glued TPU/PC layer materials Active 2031-10-29 US8911851B2 (en)

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DE200810052572 DE102008052572A1 (de) 2008-10-21 2008-10-21 Latent-reaktiv verklebte TPU/PC-Schichtstoffe
DE102008052572.3 2008-10-21
PCT/DE2009/000996 WO2010045902A1 (de) 2008-10-21 2009-07-20 Latent-reaktiv verklebte tpu/pc-schichtstoffe

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US20190135520A1 (en) * 2017-11-03 2019-05-09 The Quaker Oats Company Rigid Packages Having Peelable Hermetic Seals
WO2019193124A1 (en) 2018-04-05 2019-10-10 Adolphe Merkle Institut, University Of Fribourg Shape memory polymers

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DE102009038401A1 (de) 2009-08-24 2011-05-12 Bundesdruckerei Gmbh Folienverbund und Verfahren zur Herstellung des Folienverbundes sowie Verfahren zur Herstellung eines Sicherheitsdokumentes mit einem solchen Folienverbund
DE102010009230A1 (de) * 2010-02-25 2011-08-25 Giesecke & Devrient GmbH, 81677 Hochflexibles Folienverbundmaterial und seine Verwendung in Kartenkörpern
DE102010023218B4 (de) * 2010-06-09 2019-08-01 Bundesdruckerei Gmbh Verfahren zur Herstellung eines Wert- oder Sicherheitsdokuments mit einem Wasserzeichen
DE102011119518A1 (de) * 2011-11-25 2013-05-29 Giesecke & Devrient Gmbh Verfahren zur Herstellung von Folienverbundmaterialien mit eingeschlossenen Bauteilen
DE102016117674A1 (de) 2016-09-20 2018-03-22 Bundesdruckerei Gmbh Verfahren zur Herstellung eines Sicherheits- oder Wertprodukts mit einem diffraktiven Sicherheitselement

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WO2019193124A1 (en) 2018-04-05 2019-10-10 Adolphe Merkle Institut, University Of Fribourg Shape memory polymers

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WO2010045902A1 (de) 2010-04-29
CN102203808A (zh) 2011-09-28
PL2338133T3 (pl) 2014-02-28
DE102008052572A1 (de) 2010-04-29
US20110274883A1 (en) 2011-11-10
EP2338133A1 (de) 2011-06-29
TWI389802B (zh) 2013-03-21
TW201016486A (en) 2010-05-01
ES2435594T3 (es) 2013-12-20
WO2010045902A8 (de) 2011-06-03
PT2338133E (pt) 2013-11-07

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